Light-sensitive silver halide color-photographic material

ABSTRACT

A LIGHT-SENSITIVE SILVER HALIDE COLOR-PHOTOGRAPHIC MATERIAL INCORPORATED WITH A NOVEL MAGENTA COUPLER COMPOUND OF THE GENERAL FORMULA WHEREIN: X IS AN ALKYL OR ALKOXY GROUP WITH ONE TO FIVE CARBON ATOMS, OR HALOGEN; R IS AN ALIPHATIC HYDROCARBON RADICAL OF 12 TO 30 CARBON ATOMS; AND M IS HYDROGEN, ALKALI METAL OR AMMONIUM GROUP. THIS PHOTOGRAPHIC MATERIAL WHEN SUBJECT TO LIGHT EXPOSURE FOLLOWED BY COLOR DEVELOPMENT CAN FORM MAGENTA COLOR NEGATIVE IMAGE OR YELLOW COLOR POSITIVE IMAGE BOTH OF WHICH ARE EXCELLENT IN SPECTRAL ABSORPTION CHARACTERISTICS. THE YELLOW COLOR POSITIVE IMAGE HAS GOOD COLOR STABILITY (NO COLOR CHANGE AND NO FADING) DURING THE COLOR DEVELOPMENT AND SUBSEQUENT PROCESSING.   4-((3-(M-O3S-),4-(HO-)PHENYL)-N=N-)PYRAZOLIN-5-ONE   1-(3-(M-O3S-),(X-(PHENYLENE)-O-)PHENYL),3-(R-CO-NH-),

April 27, 1971 K. SAKAMOTQ ETAL 3,576,635

LIGHT-SENSITIVE SILVER HALIDE COLOR-PHOTOGRAPHIC MATERIAL Filed March 21, 1968 DENSITY WAVE LENGTH m l I United States Patent 3,576,635 LIGHT-SENSITIVE SILVER HALIDE COLOR- PHOTOGRAPHIC MATERIAL Kenro Sakamoto, Isabro Inoue, and Teruo Hanzawa,

Tokyo, Japan, assignors to Konishiroku Photo Industry Co., Ltd., Tokyo, Japan Filed Mar. 21, 1968, Ser. No. 714,976 Claims priority, applicatign Jiipan, Mar. 23, 1967,

Int. Cl. odsc 1/40 US. Cl. 96-100 7 Claims ABSTRACT OF THE DISCLOSURE A light-sensitive silver halide color-photographic material incorporated with a novel magenta coupler compound of the general formula This invention relates to a light-sensitive silver halide color-photographic material, characterized by that it contains a new magenta coupler of the general formula wherein X is C -C alkyl or alkoxy, or halogen atom; R is an aliphatic hydrocarbon radical of 12 to 30 carbon atoms; and M is hydrogen, alkali metal or ammonium group. 7

In the reproduction of a color original which is in the form of a negative or positive image obtained by using a light-sensitive silver halide color-photographic material, it occurs that only an image reproduction with incorrect color is obtained due to undesired absorption of dyes. In order to remove the defect of such color reproduction, various masking processes have been proposed, among which use of a light-sensitive silver halide color-photographic material with a light-sensitive layer containing a colored coupler is known effective. This-invention is concerned with an improvement in such light-sensitive silver halide color-photographic material as above.

Yellow, magenta and cyan colored images which constitute a color-photographic image have undesired absorptions at the spectral regions of green light, blue-red light and blue-green light, respectively. A magenta image has undesired absorption particularly at the spectral region of blue light, and so, it is necessary to have a yellowcolored coupler incorporated in a green-sensitive emulsion layer which can yield a magenta image upon color development, while a yellow positive image (i.e. yellow masking image) is formed by the action of unreacted coupler, thereby to corroborate undesired absorption of the magenta image at the spectral region of blue light. A colored magenta coupler which can provide such masking eifect as above and which is usable in commercial practice should fulfill the following requirements:

(a) Spectral absorption characteristics of a yellow positive masking image formed with a colored coupler is not influenced by color development;

(b) The reactivity of the coupler in color development is high and spectral absorption characteristics of the developed color image and of the masking image are satisfactory;

(c) The magenta coupler has a good dispersibility in a silver halide emulsion; and

(d) The magenta coupler can be produced in pure form and in low cost from a readily available starting material.

In order to satisfy these requirements, extensive studies have been made heretofore but without success.

In Belgian Pat. No. 664,221, for example, a colored magenta coupler of the general formula \N/ NHCO-CH-CIBHZE I CHZCOOH 3 4 In U.S.S.R. Pat. 122,676, two colored couplers are dis- (2) H closed, WhlCh have the following structural formulas. H F

s o H DH 3 t 5 f HON=N(|J (IJNHCOC11Han N s63 \H o s 0811 I M.P. 297-9 C. (decomp.) 15 CH3 H [II] HOG-N: --i--(||J-NHCO-C15Har 0: N H OaNa H0g N=N(:J- IE NHC 0-017113; f

0 on \N/ M.P. 320 C. (decomp-) s OaNa H so H EO- N=NCCNHCOC11H35 3 a II 0: N i SOsNa I SOaNa A light-sensitive photographic material having one of the above couplers [1'1] and [III] incorporated therein is superior to that comprising the coupler [I] in photographic sensitivity in usual color development. However, the negative magenta image formed by color development has undesired absorption at the spectral region of red light so that the color reproduction of a color original (5) H0 E (P0131121 over the spectral region of red light may be adversely influenced. Further, stable masking effect cannot be SOaNa expected because the unstability of the density of the yellow masking image formed with unreacted coupler. Poor solubility of these known couplers in water makes transparency of the film worse.

A colored magenta coupler used in a light-sensitive SOa & photographic material of this invention is substantially free from the above-mentioned drawbacks.

Typical colored couplers which may be used in this invention are listed below, without limiting the scope of this invention thereto. n)

M.P. 300 C. (decomp.)

SOsNa N/ S OaNa S QaNa S OaNa M.P. 291-3 C. (decomp.) Q M.P. 310 C. (deeompJ 0 CH3 7 C These compounds are new and can be synthesized by a process, as mentioned herein, which comprises diazotizing in a known manner 2-hydroxy-S-aminobenzene-sulfonic acid obtained by sulfonating p-aminophenol and coupling the diazo compound with a S-pyrazolone derivative in an aqueous or alcoholic solution of pyridine, caustic alkaline or alkali carbonate. The resulting reaction product is separated by making the reaction mixture acidic and then purified in an appropriate manner to give a color coupler of high purity. Syntheses of the above compounds are illustrated hereinafter.

SYNTHESIS OF COMPOUND (1) In a solution of 6.5 g. of sodium carbonate in 105 ml. of water, 19 g. of 2-hydr0xy- 5 arninobenzene-sulfonic acid are dissolved and 7.7 g., of sodium nitrile are added to the solution. The resulting homogeneous solution is poured into a cold solution of 20 ml. of concentrated sulfuric acid in 100 ml. of water while stirring at 5 C. Precipitate formed is collected by filtration and Washed with 100 ml. of ice water, 200 ml. of methanol and 100 ml. of ether in this order and then air-dried. Nineteen grams of diazonium salt decomposing at 173 C. are obtained.

In a solution of 62 ml. of pyridine in ml. of water, 6.2 g. of 1 [4 (4- methoxyphenoxy)-3-sulfophenyl]-3- palmitoamido-S-pyrazolone (decomposition point: 275 6 C.) are dissolved. While stirring, 3.0 g. of the above diazonium salt are added to the solution at -15 C. After stirring for 3 hours at 2025 C., 16 ml. of 10% aqueous caustic soda solution and 70 m1. of ethyl alcohol are added to the solution and stirring is effected for 10 minutes. Precipitate formed by making the solution acid with glacial acetic acid is filtered oil and Washed with 200 ml. of ethyl alcohol and then dried. Recrystallization from 30 times of volume of 80% ethyl alcohol yielded 3.1 g. of oranze-yellow powder decomposing at 291293 C.

Elementary analysis.-Calcd. for

(percent): C, 50.94; H, 5.74; N, 7.82. Found (percent): C, 50.72; H, 5.90; N, 7.60.

SNYTHESIS OF COMPOUND (2) In a solution of 60 ml. of pyridine in 6 ml. of water, 6.0 g. of 1 [4 (3 methylphenoxy) 3 sulfophenyl]-3- palmitoamido-S-pyrazolone (decomposition point: 285 C.) are dissolved. While stirring, 3,0 g. of the diazonium salt obtained in the synthesis of the compound 1) are added to the solution at 10l5 C. and the stirring is continued at 20-25 C. for 4 hours. The resulting solution is diluted with 50 ml. of ethyl alcohol and 100 ml. of water and 100 ml. of concentrated hydrochloric acid are added thereto. After cooling, precipitate formed is.

filtered off and washed with 50 ml. of ice water and then with 100 ml. of acetone. Recrystallization from 120 ml. of 70% ethyl alcohol yielded 5.0 g. of red-orange powder decomposing at 297 299 C.

Elementary analysisf-Calcd. for C H O N S (percent): C, 58.75; H, 6.19; N, 9.56. Found (percent): C, 58.95; H, 6.48; N, 9.77.

SYNTHESIS OF COMPOUND (3) In a solution of 1.6 g. of caustic soda in 160 ml. of water, 6.0 g. of 1-[2-(4-methylphenoxy)-5-sulfophenyl]- S-palmitoamido-5-pyrazolone (decomposition point: 290' C.) are dissolved and 3.0 g. of the diazonium salt obtained in the synthesis of the compound (1) are added thereto at 10-15 C. under stirring. The solution is stirred further for 3 hours at 15 20 C. and made acid with acetic acid. To the resulting solution, are added 30 g. of sodium acetate and 160 ml. of ethyl alcohol. Precipitate formed is filtered off and Washed with a solution of 10 g. of sodium acetate, 50 ml. of ethyl alcohol and 50 ml. of water and then with 100 ml. of ethyl alcohol, and dried. 3.4 g. of orange-yellow powder decomposing at above 320 C. were obtained after recrystallizing twice from 75% of ethyl alcohol.

Elementary analysis.Calcd. for

(percent): C, 52.93; H, 5.73; N, 8.13. Found (percent): C, 53.00; H, 6.01; N, 8.06.

Difference in water solubility between the color couplers used in this invention and known couplers is mentioned below.

In 3 ml. of 0.5 N-aqueous caustic soda solution, 300 mg. of each of the above couplers (1), (2), (4), (6) and the known couplers [I] and [III] are dissolved and then the resulting solution is diluted with 50 m1. of water. While stirring at 22il C., 0.05 N-aqueous citric acid solution is dropped into the solution. When the solution becomes homogeneous emulsion with precipitate formed, pH value of the solution is measured. The results obtained are shown in the Table 1 below.

TABLE 1 Sample: PH at deposition Known coupler- [III] 6.5. Coupler (1) No deposition occurs even at 4.0.

Coupler (2) Do. Coupler (4) Do. Coupler (6) Do.

From the Table 1, it is understood that the couplers used in this invention are very superior to the known couplers in water solubility.

The light-sensitive material of this invention is prepared by dissolving a color magenta coupler of the aforesaid general formula in an aqueous or alcoholic solution of caustic alkali or alkali carbonate, dispersing the resulting solution in a green-sensitized silved halide emulsion and applying the resulted dispersion on film base and then drying. An amount of the coupler added varies with the sort of a silver halide emulsion as well as the sort of a coupler used. Preferable amount of a coupler is 1-50 g. per 1 mol of silver halide emulsion and more or less amount may be acceptable. Magenta color negative image of good spectral absorption and yellow masking image resulting from unreacted coupler are formed simultaneously, when a silver halide emulsion layer containing color magenta couplers is subjected to light-exposure and then treated with a devolping bath comprising p-phenylenediamine as a devolping agent, bleached, fixed and dried.

Any color developers are commonly used for development of color-photographic materials of this invention. For example, =N,N diethyl p phenylenediamine, N- ethyl N B methansulfonamidoethyl 3 methyl-4- aminoaniline, N ethyl -N hydroxyethyl 2 methylp-phenylenediamine, N-ethyl N hydroxyethyl-p-phenylenediamine, N,N diethyl 2 methyl p phenylenediamine etc. and their sulfates, sulfites or hydrochlorides are suitable color developers.

The colored magenta coupler used in this invention, as mentioned above, has the better water solubility than the 'known coupler has. Because of this, the magenta coupler of this invention is improved in dispersibility in a silver halide photographic emulsion so that it can produce a highly transparent photographic film. Further, the film produced has a high photographic sensitivity even in the conventionally known color development, with the formation of a magenta color negative image having little absorption at the spectral region of red light. Further, a very stable masking effect can be obtained, since the spectral absorption characteristic of the yellow masking image is little influenced by the color development. Thus, the colored magenta coupler of this invention which has many advantageous features as mentioned above is very useful in' a light-sensitive color-photographic material.

The present invention is further illustrated by the following examples which are not intended to limit the scope of the present invention:

EXAMPLE 1 One gram of each of the couplers -(1), (3), (4) and (6) are dissolved respectively in ml. each of 1 N KOH aqueous solution. Each of respective solutions is diluted with water to make up 30 ml. and then dispersed into 100 ml. of a green-sensitive silver halide emulsion. The resulting dispersion is adjusted to pH 6.8 with an aqueous citric acid and then coated on a film base and dried. The thus prepared photographic films are used as test samples. On the other hand, the known couplers [I] and [IH] are individually used for the preparation of photographic films which are control samples. These samples are subjected to exposure to light through an optical wedge and then treated at 20 C. for 10 minutes with a developing solution of the following formulation:

G. N,N-diethyl p phenylenediamine sulfate 2.5 Anhydrous sodium sulfite 3.0 Sodium carbonate (monohydrate) 82.0 Potassium bromide 2.0

Water to make up 1000 ml.

After stopping and fixing, the films are washed with water for 10-15 minutes and then treated for 5 minutes with a bleaching bath of the following formulation:

. i G. Potassium ferricyanide 100 Potassium bromide 50 Water to make up 1000 ml.

Further, the films are washed with water for 10 minutes and then treated for 5 minutes with a fixing solution of the following formulation:

G. Sodium thiosulfate 250 Water to make up 1000 ml.

The films are then washed with water for 20-25 minutes and dried. The films now have a magenta color negative image and an yellow masking image. With respect to the individual films, photographic speed and absorption maximum of the masking image and magenta color negative image are measured. The results are set forth in Table 2.

In the attached drawing, there are shown the spectral absorption curve of the magenta color negative image obtained from the coupler (4) and that of the magenta color negative image obtained from the coupler [Ill].

As apparent from the data of Table 2 and the said absorption curves, the photographic film containing the magenta coupler of the present invention is highly ex- 8 cellent in photographic speed and has less red absorption when compared with the film containing the known magenta coupler.

EXAMPLE 2 Two photographic films which are test samples are prepared by using one gram of each of the couplers (l) and (6) in the same manner as in Example 1. These films are subjected to sensitometric exposure and color development in the same manner as in Example 1. The films now have a yellow masking image and a magenta color negative image. The density of the masking image of the unexposed portion when said density is measured through a blue filter (absorption maximum at 535 m is expressed as D'B. Separately, the corresponding unexposed film are treated for 5 minutes with a fixing solution containing 250 g. of sodium thiosulfate in 1000 ml. of water and then washed with water and dried. The density of the resulting image is measured as DB. The value of D'B is expressed as an index of DB which is rated as 100. As a control sample, a photographic film containing the known coupler [III] is employed. The results are set forth in Table 3.

TABLE 3 Sample DB D'B Coupler (1) 100 Coupler (6) 100 Known coupler [III] 70 EXAMPLE 3 0.2 g. of the colored coupler (2) is mixed with 0.8 g. of 1 4-(3-methylphenoxy)-3-sulfophenyl-3-palmitoamido-5- pyrazolone which is a colorless coupler. The resulting mixture is dissolved in 6 ml. of 1 N KOH aqueous solution and then diluted with water to make up 30 ml. The solution is adjusted at pH 6. 8 and dispersed in 100* ml. of a green-sensitive silver halide emulsion, which is then coated on a film base and dried.

The thus obtained photographic film has a high speed and can yield, simultaneously by color development, a magenta color negative image having good spectral absorption characteristics and a yellow positive masking image having adequate gradient.

What we claim is:

1. A light-sensitive silver halide color-photographic material, characterized by that it contains a magenta coupler of the general formula wherein X is C C alkyl or alkoxy group or halogen 10 2. A light-sensitive silver halide color-photographic 6. Alight-sensitive silver halide color-photographic mamaterial as claimed in claim 1, wherein said magenta terial as claimed in claim 1, wherein said magenta coupler coupler is a compound of the structural formula is a compound of the structural formula I HO N=N(]-|C-NHC O 015 11 O=C S OQNB H I HO N=N(|1-fiNHCO-C;5Ha1

SOsNa N S OaNa l A 15 SOQNa 3. A light-sensitive silver halide color-photographic material as claimed in claim 1, wherein said magenta coupler is a compound of the structural formula II N 7. A light-sensitive silver halide color-photographic ma- SOaH III terial as claimed 1n claim 1, wherein sald magenta coupler is a compound of the structural formula Q3 011 H S O Na CHaa 111 4. A light-sensitive silver halide color-photographic material as claimed in claim 1, wherein said magenta coupler SO Na is a compound of the structural formula 3 H I HON=N '3(|JNHCOC11H11 o= '1 1% S OaNa \N/ CHa-O Cl SOzN8 5. A light-sensitive silver halide color-photographic material as claimed in claim 1, wherein said magenta coupler ere ces Clted is a compound of the Structural forrnula P H 2 437 063 3/1948 Zeh et a1 96-100 Q N N E E NHCO 2,725,292 11/1955 Graham et al. 96-100 so Na 2,808,329 10/1957 Whitmore 96-100 N 2,848,326 8/1958 Whitmore 96-100 3,468,665 9/ 196 9 Misu et al. 96-100 3,386,830 6/1968 Yoshida et a1 96-100 SOaNa FOREIGN PATENTS 0 598,174 2/1948 Great Britain 96-100 122,676 10/1959 U.S.S.R. 96-100 J. TRAVIS BROWN, Primary Examiner US. Cl. X.R. 

